Co-doped silicooxynitrides

ABSTRACT

The invention relates to compounds of the formula (I) (Ca,Sr,Ba) 6-X (Si 1-y  Me y ) 3 (O 1-z Ma 2z ) 6 N 4 :Eu x  (I), where Me=Th, Ru and/or Os Ma═F and/or Cl, x&lt;0.5, y&lt;1 and z&lt;0.1, and to a process for the preparation of these compounds and use as phosphors and conversion phosphors for the conversion of the blue or near-UV emission from an LED.

The invention relates to compounds which consist of 6-3-6-4alkaline-earth metal silicooxynitrides which are co-doped with thorium,ruthenium, osmium, fluorine and/or chlorine, to the preparation thereof,and to the use thereof as phosphors and to LED conversion phosphors forwarm-white LEDs or so-called colour-on-demand applications.

The colour-on-demand concept is taken to mean the production of lighthaving a certain colour point by means of a pcLED (=phosphor convertedLED) using one or more phosphors. This concept is used, for example, inorder to produce certain corporate designs, for example for illuminatedcompany logos, trademarks, etc.

In order to achieve high colour spaces by means of LED TV backlighting,deep-red phosphors are necessary, which have an emission maximum in therange 620 nm-660 nm. Suitable material systems which are known to theperson skilled in the art are siliconitrides and alumosiliconitridephosphors (Xie, Sci. Technol. Adv. Mater. 2007, 8, 588-600):

1-1-2 nitrides, such as, for example, CaSiN₂:Eu²⁺ (Le Toquin, Cheetham,Chem. Phys. Lett. 2006, 423, 352), 2-5-8 nitrides, such as(Ca,Sr,Ba)₂Si₅N₈:Eu²⁺ (Li et al., Chem. Mater. 2005, 15, 4492), andalumosiliconitrides, such as (Ca,Sr)AlSiN₃:Eu²⁺ (K. Uheda et al.,Electrochem. Solid State Lett. 2006, 9, H22).

Nitridic phosphors, as mentioned above, have a series of disadvantages,which result in these materials not being available in large amounts: inparticular, the high purity necessary represents a challenge which canonly be met with considerable effort in industry. Thus, extremely lowconcentrations of carbon or oxygen result in the efficiency of thephosphors being reduced sensitively. However, it is virtually impossibleto avoid oxygen impurities, since even the starting materials, such asSi₃N₄ and the metal nitrides (alkaline-earth metal nitrides, europiumnitride), are not available in oxygen-free form. Alternative startingmaterials, such as metal hydrides, are extremely oxygen- andmoisture-sensitive, meaning that oxygen is also introduced into thephosphor via these components. Standard preparation processes, such ascarbothermal reduction and nitridation, result in carbon impurities inthe phosphor, causing this phosphor to experience greying, which reducesthe luminance.

The silicooxynitride Sr₆Si₃O₆N₄:Eu was described for the first time bySohn et al., Journ. of Electr. Soc. 155(2), J58-J61 (2008).

The object of the present invention is therefore to modify theabove-mentioned 6-3-6-4 alkaline-earth metal silicooxynitrides in such away that these compounds achieve even greater light efficiency.

Surprisingly, it has been found that the requirement for an economicallyimportant further increase in the conversion efficiency of the redsilicooxy-nitride phosphors (Ca,Sr,Ba)₆Si₃O₆N₄:Eu can be met ifco-doping with thorium, ruthenium, osmium, fluorine and/or chlorine iscarried out.

The present invention thus relates to compounds of the 6-3-6-4alkaline-earth metal silicooxynitride type with europium doping whichadditionally comprise co-dopants from the series thorium, ruthenium,osmium, fluorine and/or chlorine.

“6-3-6-4 alkaline-earth metal silicooxynitrides” are taken to meancompositions M₆Si₃O₆N₄:Eu²⁺, where M represents an alkaline-earth metalor a mixture of a plurality of alkaline-earth metals.

Preference is given to compounds of the formula I

(Ca,Sr,Ba)_(6-x)(Si_(1-y)Me _(y))₃(O_(1-z)Ma _(2z))₆N₄:Eu_(x)  (I)

whereMe=Th, Ru and/or OsMa═F and/or Clx<0.5y<1 andz<0.1.

It is preferred for the x value to be equal to 0.003 to 0.2, the y value(which stands for the atom concentration of the co-dopant Me) to beequal to 0.0001 to 0.2, and the z value to be equal to 0.0005 to 0.03.

More preferably, x=0.005 to 0.15 and/or y=0.001 to 0.02.

The greater luminance of the compounds or phosphors of the formula Iaccording to the invention compared with those of identical composition,but without the co-dopants thorium, ruthenium, osmium, fluorine and/orchlorine, can be explained by means of the theories known to the personskilled in the art. This greater luminance is produced by the highercrystal lattice quality through the presence of the halides. The halidesvery probably cause a reduction in the diffusion barriers which the ionshave to overcome in the solid-state reaction in order to be able tooccupy the desired lattice sites in the solid structure. The heavymetals Th, Ru or Os very probably cause increased absorption of thephosphor via the so-called heavy-atom effect.

The particle size of the compounds according to the invention is between50 nm and 30 μm, preferably between 1 μm and 20 μm, more preferablybetween 2 and 15 μm.

The present invention furthermore relates to a compound obtainable bymixing silicon nitride-, europium- and calcium- and/or strontium- and/orbarium-containing starting materials with at least one thorium-,osmium-, ruthenium-, fluoride- and/or chloride-containing co-dopant,which may optionally comprise a fluxing agent from the series of thealkali metal or alkaline-earth metal halides or also a borate compound,by solid-state diffusion methods and subsequent thermal aftertreatment.

The present invention furthermore relates to a process for thepreparation of a compound of the 6-3-6-4 alkaline-earth metalsilicooxynitride type with europium doping having the following processsteps:

-   -   a) preparation of an Eu-doped 6-3-6-4 alkaline-earth metal        silicooxy-nitride compound which is co-doped with thorium-,        ruthenium-, osmium-, fluoride- and/or chloride-containing        materials, by mixing at least 4 starting materials selected from        silicon nitride-, europium-, calcium-, strontium-, barium-,        thorium-, ruthenium-, osmium-, fluoride- and/or        chloride-containing materials,    -   b) thermal aftertreatment of the compound co-doped with thorium,        ruthenium, osmium, fluoride and/or chloride.    -   c) washing of the thermally aftertreated compounds with an HCl        solution and a KOH solution.

The starting materials for the preparation of the compound consist, asmentioned above, of silicon nitride (Si₃N₄), calcium hydride andeuropium fluoride and at least one Th-, Ru-, Os-, F- and Cl-containingco-dopant. Besides the preferred nitrides, hydrides and fluorides,suitable starting materials are also further inorganic and/or organicsubstances, such as cyanamides, dicyanamides, cyanides, oxalates,malonates, fumarates, carbonates, citrates, ascorbates andacetylacetonates.

The above-mentioned thermal aftertreatment (see process step b) proceedsfor a number of hours under reducing conditions, for example withforming gas (for example 90/10), pure hydrogen and/or in an ammoniaatmosphere with or without the above-mentioned atmospheres. Thetemperatures during the calcination process are between 1000° C. and1800° C., preferably 1400° C. to 1600° C., for a number of hours(preferably 8 h).

It is furthermore preferred for the phosphors to be transferred into ahigh-pressure sintering oven and calcined there at 40 to 70 bar and atemperature of 1400 to 1600° C. for 6 to 10 hours.

It is furthermore preferred for the phosphors to be subjected to hotisostatic pressing in vacuo.

It is additionally preferred for the phosphors to be washed firstly withHCl and subsequently with KOH, which eliminates amorphous SiO₂. Thiswashing step advantageously increases the emission intensity and alsothe absorption of the phosphors.

With the aid of the above-mentioned processes, it is possible to produceany desired outer shapes of the compounds or phosphors according to theinvention, such as spherical particles, flakes and structured materialsand ceramics. These shapes are summarised in accordance with theinvention under the term “shaped bodies”. The shaped body is preferablya “phosphor body”.

The present invention thus furthermore relates to a shaped bodycomprising the compounds according to the invention, which has a roughsurface which nanoparticles comprising SiO₂, TiO₂, Al₂O₃, ZnO, ZrO₂and/or Y₂O₃ or mixed oxides thereof and/or particles comprising thecompound according to the invention with or without dopants from theseries europium, osmium, ruthenium, thorium, fluorine and/or chlorine.

In a further preferred embodiment, the shaped body has a structured (forexample pyramidal) surface on the side opposite an LED chip (see WO2008/058619, Merck, which is incorporated in its full scope into thecontext of the present application by way of reference). This enables asmuch light as possible to be coupled out of the phosphor.

The structured surface on the shaped body is produced by subsequentcoating with a suitable material which is already structured, or in asubsequent step by (photo)lithographic processes, etching processes orby writing processes using energy or material beams or the action ofmechanical forces.

In a further preferred embodiment, the shaped bodies according to theinvention have, on the side opposite an LED chip, a rough surface whichcarries nanoparticles comprising SiO₂, TiO₂, Al₂O₃, ZnO₂, ZrO₂ and/orY₂O₃ or combinations of these materials and/or comprising particleshaving the phosphor composition of the formula I with or without dopantsfrom the series Th, Ru, Os, F and/or Cl. A rough surface here has aroughness of up to a few 100 nm. The coated surface has the advantagethat total reflection can be reduced or prevented and the light can bebetter coupled out of the phosphor according to the invention. (see WO2008/058619 (Merck), which is incorporated in its full scope into thecontext of the present application by way of reference)

It is furthermore preferred for the shaped bodies according to theinvention to have, on the surface facing away from the chip, a layer ofmatched refractive index which simplifies the coupling-out of theprimary radiation and or the radiation emitted by the phosphor body.

In a further preferred embodiment, the shaped bodies have a continuoussurface coating consisting of SiO₂, TiO₂, Al₂O₃, ZnO, ZrO₂ and/or Y₂O₃or mixed oxides thereof and/or of the compounds of the formula I withoutthe activator europium. This surface coating has the advantage that asuitable graduation of the refractive indices of the coating materialsenables the refractive index to be matched to the environment. In thiscase, the scattering of the light at the surface of the phosphor isreduced and a greater proportion of the light is able to penetrate intothe phosphor and be absorbed and converted there. In addition, thesurface coating of matched refractive index enables more light to becoupled out of the phosphor since total internal reflection is reduced.

In addition, a continuous layer is advantageous if the phosphor has tobe encapsulated. This may be necessary in order to counter sensitivityof the phosphor or parts thereof to diffusing water or other materialsin the immediate environment. A further reason for encapsulation with aclosed shell is thermal decoupling of the actual phosphor from the heatgenerated in the chip. This heat results in a reduction in thefluorescence light yield of the phosphor and may also influence thecolour of the fluorescence light. Finally, a coating of this typeenables the efficiency of the phosphor to be increased by preventinglattice vibrations arising in the phosphor from propagating to theenvironment.

In addition, it is preferred for the shaped body to have a poroussurface coating consisting of SiO₂, TiO₂, Al₂O₃, ZnO, ZrO₂ and/or Y₂O₃or mixed oxides thereof and/or of the compounds of the formulae I withor without dopants from the series Eu, Th, Ru, Os, F and/or Cl. Theseporous coatings offer the possibility of further reducing the refractiveindex of a single layer. Porous coatings of this type can be produced bythree conventional methods, as described in WO 03/027015, which isincorporated in its full scope into the context of the presentapplication by way of reference: the etching of glass (for examplesoda-lime glasses (see U.S. Pat. No. 4,019,884)), the application of aporous layer, and the combination of a porous layer and an etchingoperation.

In a further preferred embodiment, the shaped body has a surface whichcarries functional groups which facilitate chemical bonding or physicalbinding to the environment, preferably consisting of epoxy or siliconeresin. These functional groups can be, for example, esters or otherderivatives which are bonded via oxo groups and are able to form linksto constituents of the binders based on epoxides and/or silicones.Surfaces of this type have the advantage that homogeneous incorporationof the phosphors into the binder is facilitated. Furthermore, therheological properties of the phosphor/binder system and also the potlives can thereby be adjusted to a certain extent. Processing of themixtures is thus simplified. The term physical binding to theenvironment is used in this connection if electro-static interactionsact between the systems via charge fluctuations or partial charges.

Since the phosphor layer according to the invention applied to the LEDchip preferably consists of a mixture of silicone and homogeneousphosphor particles, and the silicone has a surface tension, thisphosphor layer is not uniform on a microscopic level or the thickness ofthe layer is not constant throughout.

The preparation of flake-form phosphors as a further preferredembodiment is carried out by conventional processes from thecorresponding metal salts and/or rare-earth salts. The preparationprocess is described in detail in EP 763573 and WO 2008/058620, whichare incorporated into the context of the present application in theirfull scope by way of reference. These flake-form phosphors can beprepared by coating a natural or synthetically prepared, highly stablesupport or a substrate comprising, for example, mica, SiO₂, Al₂O₃, ZrO₂,glass or TiO₂ flakes which has a very large aspect ratio, an atomicallysmooth surface and an adjustable thickness with a phosphor layer by aprecipitation reaction in aqueous dispersion or suspension. Besidesmica, ZrO₂, SiO₂, Al₂O₃, glass or TiO₂ or mixtures thereof, the flakesmay also consist of the phosphor material itself or be built up from onematerial. If the flake itself merely serves as support for the phosphorcoating, the latter must consist of a material which is transparent tothe primary radiation of the LED, or absorbs the primary radiation andtransfers this energy to the phosphor layer. The flake-form phosphorsare dispersed in a resin (for example silicone or epoxy resin), and thisdispersion is applied to the LED chip.

The flake-form phosphors can be prepared on a large industrial scale inthicknesses of 50 nm to about 20 μm, preferably between 150 nm and 5 μm.The diameter here is from 50 nm to 20 μm. It generally has an aspectratio (ratio of the diameter to the particle thickness) of 1:1 to 400:1and in particular 3:1 to 100:1. The flake dimensions (length×width) aredependent on the arrangement. Flakes are also suitable as centres ofscattering within the conversion layer, in particular if they haveparticularly small dimensions.

The surface of the flake-form phosphor according to the invention facingthe LED chip can be provided with a coating which has an antireflectionaction with respect to the primary radiation emitted by the LED chip.This results in a reduction in back-scattering of the primary radiation,enabling the latter to be coupled better into the phosphor bodyaccording to the invention.

Suitable for this purpose are, for example, coatings of matchedrefractive index, which must have a following thickness d: d=[wavelengthof the primary radiation of the LED chip/(4*refractive index of thephosphor ceramic)], see, for example, Gerthsen, Physik [Physics],Springer Verlag, 18th Edition, 1995. This coating may also consist ofphotonic crystals. Which also includes structuring of the surface of theflake-form phosphor in order to achieve certain functionalities.

The shaped bodies according to the invention in the form of ceramicbodies are produced analogously to the process described in WO2008/017353 (Merck), which is incorporated in its full scope into thecontext of the present application by way of reference. In this process,the phosphor is prepared by mixing the corresponding starting materialsand dopants, subsequently subjected to isostatic pressing and applieddirectly to the surface of the chip in the form of a homogeneous thinand non-porous flake or at a distance from the chip (remote phosphorconcept). The respective arrangement depends, inter alia, on thearchitecture of the LED device, where the person skilled in the art isable to select the advantageous arrangement.

There is thus no location-dependent variation of the excitation andemission of the phosphor, which means that the LED provided therewithemits a homogeneous light cone of constant colour and has high lightoutput. The ceramic phosphor bodies can be produced on a largeindustrial scale, for example, as flakes in thicknesses from a few 100nm to about 500 μm. The flake dimensions (length×width) are dependent onthe arrangement. In the case of direct application to the chip, the sizeof the flake should be selected in accordance with the chip dimensions(from about 100 μm* 100 μm to several mm²) with a certain oversize ofabout 10% to 30% of the chip surface with a suitable chip arrangement(for example flip-chip arrangement) or correspondingly. If the phosphorflake is installed over a finished LED, all of the exiting light conepasses through the flake.

The side surfaces of the ceramic phosphor body can be coated with alight metal or noble metal, preferably aluminium or silver. The metalcoating has the effect that light does not exit laterally from thephosphor body. Light exiting laterally can reduce the light current tobe coupled out of the LED. The metal coating of the ceramic phosphorbody is carried out in a process step after the isostatic pressing togive rods or flakes, where a cutter of the rods or flakes to therequisite size can optionally be carried out before the metal coating.To this end, the side surfaces are wetted, for example, with a solutioncomprising silver nitrate and glucose and subsequently exposed to anammonia atmosphere at elevated temperature. A silver coating, forexample, forms on the side surfaces in the process.

Alternatively, currentless metallisation processes are also suitable,see, for example, Hollemann-Wiberg, Lehrbuch der Anorganischen Chemie[Text-book of Inorganic Chemistry], Walter de Gruyter Verlag or UllmannsEnzyklopädie der chemischen Technologie [Ullmann's Encyclopaedia ofChemical Technology].

The ceramic phosphor body can, if necessary, be fixed to the baseboardof an LED chip using a water-glass solution.

In a further embodiment, the ceramic phosphor body has, on the sideopposite an LED chip, a structured (for example pyramidal) surface. Thisenables as much light as possible to be coupled out of the phosphorbody. The structured surface on the phosphor body is produced bycarrying out the isostatic pressing using a compression mould having astructured pressure plate and thus embossing a structure into thesurface. Structured surfaces are desired if the aim is to produce thethinnest possible phosphor bodies or flakes. The pressing conditions areknown to the person skilled in the art (see J. Kriegsmann, Technischekeramische Werkstoffe [Technical Ceramic Materials], Chapter 4,Deutscher Wirtschaftsdienst, 1998). It is important that the pressingtemperatures used are ⅔ to ⅚ of the melting point of the substance to bepressed.

The present invention furthermore relates to a process for theproduction of a shaped body, preferably a phosphor body, having thefollowing process steps:

-   -   a) preparation of a europium-doped 6-3-6-4 alkaline-earth metal        silicooxy-nitride compound which is co-doped thorium-,        ruthenium, osmium-, fluoride and/or chloride-containing        materials, by mixing at least 4 starting materials selected from        silicon nitride-, europium-, calcium-, strontium-, barium-,        ruthenium-, thorium-, osmium, fluoride- and/or        chloride-containing materials,    -   b) thermal aftertreatment of the compound co-doped with        thorium-, ruthenium, osmium, fluoride and/or chloride- and        formation of a shaped body having a rough surface,    -   c) coating of the surface with nanoparticles comprising SiO₂        TiO₂, Al₂O₃, ZnO, ZrO₂ and/or Y₂O₃ or mixed oxides thereof or        with nanoparticles comprising the compounds according to the        invention.

In addition, the excitability of the phosphors according to theinvention extends over a broad range, which extends from about 350 nm to530 nm, preferably 430 nm to about 500 nm. These phosphors are thussuitable not only for excitation by UV- or blue-emitting primary lightsources, such as LEDs or conventional discharge lamps (for example basedon Hg), but also for light sources as such which utilise the blue In³⁺line at 451 nm.

The present invention furthermore relates to a lighting unit having atleast one primary light source whose emission maximum or maxima extendsin the range 250 nm to 530 nm, preferably 350 nm to about 500 nm. Arange between 440 and 480 nm is particularly preferred, with the primaryradiation being partially or fully converted into longer-wavelengthradiation by the compounds or phosphors according to the invention. Thislighting unit is preferably white-emitting or emits light having acertain colour point (colour-on-demand principle). Preferred embodimentsof the lighting units according to the invention are depicted in FIGS. 1to 7.

In a preferred embodiment of the lighting unit according to theinvention, the light source is a luminescent indium aluminium galliumnitride, in particular of the formula In_(i)Ga_(j)Al_(k)N, where 0≦i,0≦j, 0≦k, and 1+j+k=1. Possible forms of light sources of this type areknown to the person skilled in the art. These can be light-emitting LEDchips of various structure.

In a further preferred embodiment of the lighting unit according to theinvention, the light source is a luminescent arrangement based on ZnO,TCO (transparent conducting oxide), ZnSe or SiC or also an arrangementbased on an organic light-emitting layer (OLED).

In a further preferred embodiment of the lighting unit according to theinvention, the light source is a source which exhibitselectroluminescence and/or photoluminescence. The light source mayfurthermore also be a plasma or discharge source.

The phosphors according to the invention can either be dispersed in aresin (for example epoxy or silicone resin) or, given suitable sizeratios, arranged directly on the primary light source or alternativelyarranged remote therefrom, depending on the application (the latterarrangement also encompasses “remote phosphor technology”). Theadvantages of remote phosphor technology are known to the person skilledin the art and are revealed, for example, by the following publication:Japanese Journ. of Appl. Phys. Vol. 44, No. 21 (2005). L649-L651.

In a further embodiment, it is preferred for the optical coupling of thelighting unit between the phosphor and the primary light source to beachieved by a light-conducting arrangement. It is thus possible for theprimary light source to be installed at a central location and to beoptically coupled to the phosphor by means of light-conducting devices,such as, for example, optical fibres. In this way, it is possible toachieve lights adapted to the lighting wishes which merely consist ofone or various phosphors, which can be arranged to form a light screen,and an optical waveguide, which is coupled to the primary light source.In this way, it is possible to place a strong primary light source at alocation which is favourable for electrical installation and to installlights comprising phosphors which are coupled to the optical waveguidesat any desired locations without further electrical cabling, but insteadonly by laying optical waveguides.

The present invention furthermore relates to the use of the compoundsand shaped bodies according to the invention as phosphors or phosphorbodies.

The present invention furthermore relates to the use of the compoundsaccording to the invention for the partial or complete conversion of theblue or near-UV emission from a luminescent diode.

Preference is furthermore given to the use of the compounds according tothe invention for conversion of the blue or near-UV emission intovisible white radiation. Preference is furthermore given to the use ofthe compounds according to the invention for conversion of the primaryradiation into a certain colour point in accordance with the“colour-on-demand” concept.

The compounds of the formula I according to the invention can beemployed individually or as a mixture with the following phosphors whichare familiar to the person skilled in the art:

Ba₂SiO₄:Eu²⁺, BaSi₂O₆:Pb²⁺, Ba_(x)Sri_(1-x)F₂:Eu²⁺, BaSrMgSi₂O₇:Eu²⁺,BaTiP₂O₇, (Ba,Ti)₂P₂O₇:Ti, Ba₃WO₆:U, BaY₂F₈ Er³⁺, Yb⁺, Be₂SiO₄:Mn²⁺,Bi₄Ge₃Oi₂, CaAl₂O₄:Ce³⁺, CaLa₄O₇:Ce³⁺, CaAl₂O₄:Eu²⁺, CaAl₂O₄:Mn²⁺,CaAl₄O₇:Pb²⁺, Mn²⁺, CaAl₂O₄:Tb³⁺, Ca₃Al₂Si₃O₁₂:Ce³⁺, Ca₃Al₂Si₃Oi₂:Ce³⁺,Ca₃Al₂Si₃O,₂:Eu²⁺, Ca₂B₅O₉Br:Eu²⁺, Ca₂B₆O₆Cl:Eu²⁺, Ca₂B₆O₆Cl:Pb²⁺,CaB₂O₄:Mn²⁺, Ca₂B₂O₆:Mn²⁺, CaB₂O₄:Pb²⁺, CaB₂P₂O₆:Eu²⁺, Ca₆B₂SiO₁₀:Eu³⁺,Ca_(0.6)Ba_(0.5)Al₁₂O₁₉:Ce³⁺, Mn²⁺, Ca₂Ba₃(PO4)₃Cl:Eu²⁺, CaBr₂:Eu²⁺ inSiO₂, CaCl₂:Eu²⁺ in SiO₂, CaCl₂:Eu²⁺, Mn²⁺ in SiO₂, CaF₂:Ce³⁺,CaF₂:Ce³⁺, Mn²⁺, CaF₂:Ce³⁺, Tb³⁺, CaF₂:Eu²⁺, CaF₂:Mn²⁺, CaF₂:U,CaGa₂O₄:Mn²⁺, CaGa₄O₇:Mn²⁺, CaGa₂S₄:Ce³⁺, CaGa₂S₄:Eu²⁺, CaGa₂S₄:Mn²⁺,CaGa₂S₄:Pb²⁺, CaGeO₃:Mn²⁺, CaI₂:Eu²⁺ in SiO₂, CaI₂:Eu²⁺, Mn²⁺ in SiO₂,CaLaBO₄:Eu³⁺, CaLaB₃O₇:Ce³⁺, Mn²⁺, Ca₂La₂BO_(6.5):Pb²⁺, Ca₂MgSi₂O₇,Ca₂MgSi₂O₇:Ce³⁺, CaMgSi₂O₆:Eu²⁺, Ca₃MgSi₂O₈:Eu²⁺, Ca₂MgSi₂O₇:Eu²⁺,CaMgSi₂O₆:Eu²⁺, Mn²⁺, Ca₂MgSi₂O₇:Eu²⁺, Mn²⁺, CaMoO₄, CaMoO₄:Eu³⁺,CaO:Bi³⁺, CaO:Cd²⁺, CaO:Cu⁺, CaO:Eu³⁺, CaO:Eu³⁺, Na⁺, CaO:Mn²⁺,CaO:Pb²⁺, CaO:Sb³⁺, CaO:Sm³⁺, CaO:Tb³⁺, CaO:Tl, CaO:Zn²⁺, Ca₂P₂O₇:Ce³⁺,α-Ca₃(PO₄)₂:Ce³⁺, β-Ca₃(PO₄)₂:Ce³⁺, Ca₆(PO₄)₃Cl:Eu²⁺, Ca₆(PO₄)₃Cl:Mn²⁺,Ca₆(PO₄)₃Cl:Sb³⁺, Ca₆(PO₄)₃Cl:Sn²⁺, β-Ca₃(PO₄)₂:Eu²⁺, Mn²⁺,Ca₆(PO₄)₃F:Mn²⁺, Ca_(s)(PO₄)₃F:Sb³⁺, Ca_(s)(PO₄)₃F:Sn²⁺,α-Ca₃(PO₄)₂:Eu²⁺, β-Ca₃(PO₄)₂:Eu²⁺, Ca₂P₂O₇:Eu²⁺, Ca₂P₂O₇:Eu²⁺, Mn²⁺,CaP₂O₆:Mn²⁺, α-Ca₃(PO₄)₂:Pb²⁺, α-Ca₃(PO₄)₂:Sn²⁺, β-Ca₃(PO₄)₂:Sn²⁺,β-Ca₂P₂O₇:Sn, Mn, α-Ca₃(PO₄)₂:Tr, CaS:Bi³⁺, CaS:Bi³⁺, Na, CaS:Ce³⁺,CaS:Eu²⁺, CaS:Cu⁺, Na⁺, CaS:La³⁺, CaS:Mn²⁺, CaSO₄:Bi, CaSO₄:Ce³⁺,CaSO₄:Ce³⁺, Mn²⁺, CaSO₄:Eu²⁺, CaSO₄:Eu²⁺, Mn²⁺, CaSO₄:Pb²⁺, CaS:Pb²⁺,CaS:Pb²⁺, Cl, CaS:Pb²⁺, Mn²⁺, CaS:Pr³⁺, Pb²⁺, Cl, CaS:Sb³⁺, CaS:Sb³⁺,Na, CaS:Sm³⁺, CaS:Sn²⁺, CaS:Sn²⁺, F, CaS:Tb³⁺, CaS:Tb³⁺, Cl, CaS:Y³⁺,CaS:Yb²⁺, CaS:Yb²⁺, Cl, CaSiO₃:Ce³⁺, Ca₃SiO₄Cl₂:Eu²⁺, Ca₃SiO₄Cl₂:Pb²⁺,CaSiO₃:Eu²⁺, CaSiO₃:Mn²⁺, Pb, CaSiO₃:Pb²⁺, CaSiO₃:Pb²⁺, Mn²⁺,CaSiO₃:Ti⁴⁺, CaSr₂(PO₄)₂:Bi³⁺, β-(Ca,Sr)₃(PO₄)₂:Sn²⁺Mn²⁺,CaTi_(0.6)Al_(0.1)O₃:Bi³⁺, CaTiO₃:Eu³⁺, CaTiO₃Pr³⁺, Ca₅(VO₄)₃Cl, CaWO₄,CaWO₄:Pb²⁺, CaWO₄:W, Ca₃WO₆:U, CaYAlO₄:Eu³⁺, CaYBO₄:Bi³⁺, CaYBO₄:Eu³⁺,CaYB_(0.8)O_(3.7):Eu³⁺, CaY₂ZrO₆:Eu³⁺, (Ca,Zn,Mg)₃(PO₄)₂:Sn, CeF₃,(Ce,Mg)BaAl₁₁O₁₈:Ce, (Ce,Mg)SrAl₁₁O₁₈:Ce, CeMgAl₁₁O₁₆:Ce:Tb,Cd₂B₆O₁₁:Mn²⁺, CdS:Ag⁺, Cr, CdS:In, CdS:In, CdS:In, Te, CdS:Te, CdWO₄,CsF, CsI, CsI:Na⁺, CsI:Tl, (ErCl₃)_(0.25)(BaCl₂)_(0.75), GaN:Zn,Gd₃Ga₆O₁₂:Cr³⁺, Gd₃Ga₅O₁₂:Cr, Ce, GdNbO₄:Bi³⁺, Gd₂O₂S:Eu³⁺, Gd₂O₂Pr³⁺,Gd₂O₂S:Pr, Ce, F, Gd₂O₂S:Tb³⁺, Gd₂SiO₆:Ce³⁺, KAl₁₁O₁₇:Tl⁺,KGa₁₁O₁₇:Mn²⁺, K₂La₂Ti₃O₁₀:Eu, KMgF₃:Eu²⁺, KMgF₃:Mn²⁺, K₂SiF₆:Mn⁴⁺,LaAl₃B₄O₁₂:Eu³⁺, LaAIB₂O₆:Eu³⁺, LaAlO₃:Eu³⁺, LaAlO₃:Sm³⁺, LaAsO₄:Eu³⁺,LaBr₃:Ce³⁺, LaBO₃:Eu³⁺, (La,Ce,Tb)PO₄:Ce:Tb, LaCl₃:Ce³⁺, La₂O₃:Bi³⁺,LaOBr:Tb³⁺, LaOBr:Tm³⁺, LaOCl:Bi³⁺, LaOCl:Eu³⁺, LaOF:Eu³⁺, La₂O₃:Eu³⁺,La₂O₃:Pr³⁺, La₂O₂S:Tb³⁺, LaPO₄:Ce³⁺, LaPO₄:Eu³⁺, LaSiO₃Cl:Ce³⁺,LaSiO₃Cl:Ce³⁺, Tb³⁺, LaVO₄:Eu³⁺, La₂W₃O₁₂:Eu³⁺, LiAlF₄:Mn²⁺,LiAl₆O₈:Fe³⁺, LiAlO₂:Fe³⁺, LiAlO₂:Mn²⁺, LiAl₆O₈:Mn²⁺, Li₂CaP₂O₇:Ce³⁺,Mn²⁺, LiCeBa₄Si₄O₁₄:Mn²⁺, LiCeSrBa₃Si₄O₁₄:Mn²⁺, LiInO₂:Eu³⁺,LiInO₂:Sm³⁺, LiLaO₂:Eu³⁺, LuAlO₃:Ce³⁺, (Lu,Gd)₂SiO₆:Ce³⁺, Lu₂SiO₆:Ce³⁺,Lu₂Si₂O₇:Ce³⁺, LuTaO₄:Nb⁵⁺, Lu_(1-x)Y_(x)AlO₃:Ce³⁺, MgAl₂O₄:Mn²⁺,MgSrAl₁₀O₁₇:Ce, MgB₂O₄:Mn²⁺, MgBa₂(PO₄)₂:Sn²⁺, MgBa₂(PO₄)₂:U,MgBaP₂O₇:Eu²⁺, MgBaP₂O₇:Eu²⁺, Mn²⁺, MgBa₃Si₂O₈:Eu²⁺, MgBa(SO₄)₂:Eu²⁺,Mg₃Ca₃(PO₄)₄:Eu²⁺, MgCaP₂O₇:Mn²⁺, Mg₂Ca(SO₄)₃:Eu²⁺, Mg₂Ca(SO₄)₃:Eu²⁺,Mn², MgCeAl_(n)O₁₉:Tb³⁺, Mg₄(F)GeO₆:Mn²⁺, Mg₄(F)(Ge,Sn)O₆:Mn²⁺,MgF₂:Mn²⁺, MgGa₂O₄:Mn²⁺, Mg₈Ge₂O₁₁F₂:Mn⁴⁺, MgS:Eu²⁺, MgSiO₃:Mn²⁺,Mg₂SiO₄:Mn²⁺, Mg₃SiO₃F₄:Ti⁴⁺, MgSO₄:Eu²⁺, MgSO₄:Pb²⁺, MgSrBa₂Si₂O₇:Eu²⁺,MgSrP₂O₇:Eu²⁺, MgSr₆(PO₄)₄:Sn²⁺, MgSr₃Si₂O₈:Eu²⁺, Mn²⁺,Mg₂Sr(SO₄)₃:Eu²⁺, Mg₂TiO₄:Mn⁴⁺, MgWO₄, MgYBO₄:Eu³⁺, Na₃Ce(PO₄)₂:Tb³⁺,NaI:Tl, Na_(1.23)K_(O.42)Eu_(0.12)TiSi₄O₁₁:Eu³⁺,Na_(1.23)K_(0.42)Eu_(0.12)TiSi₅O₁₃.xH₂O:Eu³⁺,Na_(1.29)K_(0.46)Er_(0.08)TiSi₄O₁₁:Eu³⁺, Na₂Mg₃Al₂Si₂O₁₀:Tb,Na(Mg_(2-x)Mn_(x))LiSi₄O₁₀F₂:Mn, NaYF₄:Er³⁺, Yb³⁺, NaYO₂:Eu³⁺,P46(70%)+P47 (30%), SrAl₁₂O₁₆:Ce³⁺, Mn²⁺, SrAl₂O₄:Eu²⁺, SrAl₄O₇:Eu³⁺,SrAl₁₂O₁₉:Eu²⁺, SrAl₂S₄:Eu²⁺, Sr₂B₆O₉Cl:Eu²⁺, SrB₄O₇:Eu²⁺(F,Cl,Br),SrB₄O₇:Pb²⁺, SrB₄O₇:Pb²⁺, Mn²⁺, SrB₈O₁₃:Sm²⁺,Sr_(x)Ba_(y)Cl_(z)Al₂O_(4-z/2):Mn²⁺, SrBaSiO₄:Eu²⁺, Sr(Cl,Br,I)₂:Eu²⁺ inSiO₂, SrCl₂:Eu²⁺ in SiO₂, Sr₅Cl(PO₄)₃:Eu, Sr_(w)F_(x)(B₄O_(6.5):Eu²⁺,Sr_(w)F_(x)B_(y)O_(z):Eu²⁺, Sm²⁺, SrF₂:Eu²⁺, SrGa₁₂O₁₉:Mn²⁺,SrGa₂S₄:Ce³⁺, SrGa₂S₄:Eu²⁺, SrGa₂S₄:Pb²⁺, SrIn₂O₄:Pr³⁺, Al³⁺,(Sr,Mg)₃(PO₄)₂:Sn, SrMgSi₂O₆:Eu²⁺, Sr₂MgSi₂O₇:Eu²⁺, Sr₃MgSi₂O₈:Eu²⁺,SrMoO₄:U, SrO.3B₂O₃:Eu²⁺, Cl, β-SrO.3B₂O₃:Pb²⁺, β-SrO.3B₂O₃:Pb²⁺, Mn²⁺,α-SrO.3B₂O₃:Sm²⁺, Sr₆P₆BO₂₀:Eu, Sr₆(PO₄)₃Cl:Eu²⁺, Sr₆(PO₄)₃Cl:Eu²⁺,Pr³⁺, Sr₆(PO₄)₃Cl:Mn²⁺, Sr₆(PO₄)₃Cl:Sb³⁺, Sr₂P₂O₇:Eu²⁺,β-Sr₃(PO₄)₂:Eu²⁺, Sr₆(PO₄)₃F:Mn²⁺, Sr₆(PO₄)₃F:Sb³⁺, Sr₆(PO₄)₃F:Sb³⁺,Mn²⁺, Sr₆(PO₄)₃F:Sn²⁺, Sr₂P₂O₇:Sn²⁺, β-Sr₃(PO₄)₂:Sn²⁺, β-Sr₃(PO₄)₂:Sn²⁺,Mn²⁺(Al), SrS:Ce³⁺, SrS:Eu²⁺, SrS:Mn²⁺, SrS:Cu⁺, Na, SrSO₄:Bi,SrSO₄:Ce³⁺, SrSO₄:Eu²⁺, SrSO₄:Eu²⁺, Mn²⁺, Sr₅Si₄O₁₀Cl₆:Eu²⁺,Sr₂SiO₄:Eu²⁺, SrTiO₃:Pr³⁺, SrTiO₃:Pr³⁺, Al³⁺, Sr₃WO₆:U, SrY₂O₃:Eu³⁺,ThO₂:Eu³⁺, ThO₂:Pr³⁺, ThO₂:Tb³⁺, YAl₃B₄O₁₂:Bi³⁺, YAl₃B₄O₁₂:Ce³⁺,YAl₃B₄O₁₂:Ce³⁺, Mn, YAl₃B₄O₁₂:Ce³⁺, Tb³⁺, YAl₃B₄O₁₂:Eu³⁺,YAl₃B₄O₁₂:Eu³⁺, Cr³⁺, YAl₃B₄O₁₂:Th⁴⁺, Ce³⁺, Mn²⁺, YAlO₃:Ce³⁺,Y₃Al₆O₁₂:Ce³⁺, Y₃Al₆O₁₂:Cr³⁺, YAlO₃:Eu³⁺, Y₃Al₅O₁₂:Eu³⁺, Y₄Al₂O₉:Eu³⁺,Y₃Al₆O₁₂:Mn⁴⁺, YAlO₃:Sm³⁺, YAlO₃:Tb³⁺, Y₃Al₆O₁₂:Tb³⁺, YAsO₄:Eu³⁺,YBO₃:Ce³⁺, YBO₃:Eu³⁺, YF₃:Er³⁺, Yb³⁺, YF₃:Mn²⁺, YF₃:Mn²⁺, Th⁴⁺,YF₃:Tm³⁺, Yb³⁺, (Y,Gd)BO₃:Eu, (Y,Gd)BO₃:Tb, (Y,Gd)₂O₃:Eu³⁺,Y_(1.34)Gd_(0.60)O₃(Eu,Pr), Y₂O₃:Bi³⁺, YOBrEu³⁺, Y₂O₃:Ce, Y₂O₃:Er³⁺,Y₂O₃:Eu³⁺(YOE), Y₂O₃:Ce³⁺, Tb³⁺, YOCl:Ce³⁺, YOCl:Eu³⁺, YOF:Eu³⁺,YOF:Tb³⁺, Y₂O₃:Ho³⁺, Y₂O₂S:Eu³⁺, Y₂O₂S:Pr³⁺, Y₂O₂S:Tb³⁺, Y₂O₃:Tb³⁺,YPO₄:Ce³⁺, YPO₄:Ce³⁺, Tb³⁺, YPO₄:Eu³⁺, YPO₄:Mn²⁺, Th⁴⁺, YPO₄:V⁵⁺,Y(P,V)O₄:Eu, Y₂SiO₆:Ce³⁺, YTaO₄, YTaO₄:Nb⁵⁺, YVO₄:Dy³⁺, YVO₄:Eu³⁺,ZnAl₂O₄:Mn²⁺, ZnB₂O₄:Mn²⁺, ZnBa₂S₃:Mn²⁺, (Zn,Be)₂SiO₄:Mn²⁺,Zn_(0.4)Cd_(0.6)S:Ag, Zn_(0.6)Cd_(0.4)S:Ag, (Zn, Cd)S:Ag, Cl, (Zn,Cd)S:Cu, ZnF₂:Mn²⁺, ZnGa₂O₄, ZnGa₂O₄:Mn²⁺, ZnGa₂S₄:Mn²⁺, Zn₂GeO₄:Mn²⁺,(Zn,Mg)F₂:Mn²⁺, ZnMg₂(PO₄)₂:Mn²⁺, (Zn,Mg)₃(PO₄)₂:Mn²⁺, ZnO:Al³⁺, Ga³⁺,ZnO:Bi³⁺, ZnO:Ga³⁺, ZnO:Ga, ZnO—CdO:Ga, ZnO:S, ZnO:Se, ZnO:Zn, ZnS:Ag,Cu, Cl, ZnS:Ag, Ni, ZnS:Au, In, ZnS—CdS (25-75), ZnS—CdS (50-50),ZnS—CdS (75-25), ZnS—CdS:Ag, Br, Ni, ZnS—CdS:Ag⁺, Cl, ZnS—CdS:Cu, Br,ZnS—CdS:Cu, I, ZnS:Cl⁻, ZnS:Eu²⁺, ZnS:Cu, ZnS:Cu⁺, Al³⁺, ZnS:Cu⁺, Cl⁻,ZnS:Cu, Sn, ZnS:Eu²⁺, ZnS:Mn²⁺, ZnS:Mn, Cu, ZnS:Mn²⁺, Te²⁺, ZnS:P,ZnS:P³⁻, Cl⁻, ZnS:Pb²⁺, ZnS:Pb²⁺, Cl⁻, ZnS:Pb, Cu, Zn₃(PO₄)₂:Mn²⁺,Zn₂SiO₄:Mn²⁺, Zn₂SiO₄:Mn²⁺, As⁵⁺, Zn₂SiO₄:Mn, Sb₂O₂, Zn₂SiO₄:Mn²⁺, P,Zn₂SiO₄:Ti⁴⁺, ZnS:Sn²⁺, ZnS:Sn, Ag, ZnS:Sn²⁺, Li⁺, ZnS:Te, Mn,ZnS—ZnTe:Mn²⁺, ZnSe:Cu⁺, Cl, ZnWO₄

The following examples are intended to illustrate the present invention.However, they should in no way be regarded as limiting. All compounds orcomponents which can be used in the compositions are either known andcommercially available or can be synthesised by known methods. Thetemperatures indicated in the examples are always in ° C. It furthermoregoes without saying that, both in the description and also in theexamples, the added amounts of the components in the compositions alwaysadd up to a total of 100%. Percentage data given should always beregarded in the given connection. However, they usually always relate tothe weight of the part-amount or total amount indicated.

EXAMPLES Example 1 Preparation of 5 g of Sr_(5.94)Eu_(0.06)Si₃O₆N₄

6.8112 g of SrC₂O₄ (Alfa Aesar, 95%), 0.0689 g of Eu₂O₃ (Treibacher,99.99%) and 0.9159 g of α-Si₃N₄ (UBE, 99%) are thoroughly combined withone another in an agate mortar in a glovebox filled with dry N₂. Thecrude substance mixture obtained in this way is transferred into anAl₂O₃ boat lined with Mo foil. The mixture is heated at 1200-1600° C.for 8 hours under an N₂/H₂/NH₃ atmosphere

Example 2 Preparation of 5 g of Sr_(5.94)Eu_(0.06)Si₃O_(5.88)N₄F_(0.24)

6.6736 g of SrC₂O₄ (Alfa Aesar, 95%), 0.0689 g of Eu₂O₃ (Treibacher,99.99%), 0.0984 g of SrF₂ (Aldrich, 99.998%) and 0.9159 g of α-Si₃N₄(UBE, 99%) are thoroughly combined with one another in an agate mortarin a glovebox filled with dry N₂. The crude substance mixture obtainedin this way is transferred into an Al₂O₃ boat lined with Mo foil. Themixture is heated at 1200-1600° C. for 8 hours under an N₂/H₂/NH₃atmosphere.

Example 3 Preparation of 5 g of Sr_(5.94)Eu_(0.06)Si₃O_(5.88)N₄Cl_(0.24)

6.6168 g of SrC₂O₄ (Alfa Aesar, 95%), 0.0683 g of Eu₂O₃ (Treibacher,99.99%), 0.1231 g of SrCl₂ (Alfa Aesar, 99.5%) and 0.9081 g of α-Si₃N₄(UBE, 99%) are thoroughly combined with one another in an agate mortarin a glovebox filled with dry N₂. The crude substance mixture obtainedin this way is transferred into an Al₂O₃ boat lined with Mo foil. Themixture is heated at 1200-1600° C. for 8 hours under an N₂/H₂/NH₃atmosphere.

Example 4 Preparation of 5 g of Sr_(5.82)Th_(0.06)Eu_(0.06)Si₃O₆N₄

6.6444 g of SrC₂O₄ (Alfa Aesar, 95%), 0.0686 g of Eu₂O₃ (Treibacher,99.99%), 0.1030 g of ThO₂ (Merck, 99%) and 0.9119 g of α-Si₃N₄ (UBE,99%) are thoroughly combined with one another in an agate mortar in aglovebox filled with dry N₂. The crude substance mixture obtained inthis way is transferred into an Al₂O₃ boat lined with Mo foil. Themixture is heated at 1200-1600° C. for 8 hours under an N₂/H₂/NH₃atmosphere.

Example 5 Preparation of 5 g of Sr_(5.82)Os_(0.06)Eu_(0.06)Si₃O₆N₄

6.6658 g of SrC₂O₄ (Alfa Aesar, 95%), 0.0688 g of Eu₂O₃ (Treibacher,99.99%), 0.0869 g of OsO₂ (Alfa Aesar, Os 83% min) and 0.9148 g ofα-Si₃N₄ (UBE, 99%) are thoroughly combined with one another in an agatemortar in a glovebox filled with dry N₂. The crude substance mixtureobtained in this way is transferred into an Al₂O₃ boat lined with Mofoil. The mixture is heated at 1200-1600° C. for 8 hours under anN₂/H₂/NH₃ atmosphere.

Example 6 Preparation of 5 g of Sr_(5.82)Ru_(0.06)Eu_(0.06)Si₃O₆N₄

6.7129 g of SrC₂O₄ (Alfa Aesar, 95%), 0.0693 g of Eu₂O₃ (Treibacher,99.99%), 0.0524 g of RuO₂ (Alfa Aesar, 99.9%) and 0.9213 g of α-Si₃N₄(UBE, 99%) are thoroughly combined with one another in an agate mortarin a glovebox filled with dry N₂. The crude substance mixture obtainedin this way is transferred into an Al₂O₃ boat lined with Mo foil. Themixture is heated at 1200-1600° C. for 8 hours under an N₂/H₂/NH₃atmosphere.

Example 7 High-Pressure Sintering of the Phosphors from Examples 1-6

In each case, 5 g of the compounds from Examples 1-6 are introduced intoan MO crucible and transferred into a high-pressure sintering oven. Thesamples are heated therein to a temperature of 1400-1600° C. at anitrogen pressure of 40-70 bar and a heating ramp of 5-10 K/min. Thehold time is 6-10 hours.

Example 8 Hot Isostatic Pressing of the Phosphors from Examples 1-6

In each case, 5 g of the compounds from Examples 1-6 are transferredinto an isostatic hot press. The hot press is placed under vacuum, andthe temperature is raised to 200° C. The temperature is subsequentlyraised to 1400-1600° C. at 5-10 K/min, and at the same time the pressureis adjusted to values between 50 and 200 MPa. The hold time is 6-10hours.

Example 9 Washing of the Phosphors from Examples 1-8

In each case, 5 g of the compounds from Examples 1-8 are suspended in100 ml of 1 molar hydrochloric acid and stirred at room temperature for3 hours. The residue is subsequently filtered off with suction andwashed with deionised water until neutral. The washed residue is thensuspended in 100 ml of a 1 molar KOH solution and stirred for a further30 minutes. The residue is subsequently filtered off with suction andagain washed with deionised water until neutral.

TABLE 1 Optical properties of Sr_(5.94)Eu_(0.06)Si₃O₆N₄:Eu (asreference) and co- doped phosphors according to the inventionComposition Emission max. [nm] CIE 1931 x, y Sr_(5.94)Eu_(0.06)Si₃O₆N₄624 0.623 0.376 Sr_(5.94)Eu_(0.06)Si₃O_(5.88)N₄F_(0.24) 623 0.622 0.377Sr_(5.94)Eu_(0.06)Si₃O_(5.88)N₄Cl_(0.24) 625 0.625 0.374Sr_(5.94)Ru_(0.06)Eu_(0.06)Si₃O₆N₄ 624 0.623 0.376Sr_(5.94)Th_(0.06)Eu_(0.06)Si₃O₆N₄ 625 0.621 0.378

DESCRIPTION OF THE FIGURES

The invention will be explained in greater detail below with referenceto a number of working examples. The figures show the following:

FIG. 1: shows a COB (chip on board) package of the InGaN type, whichserves as light source (LED) for white light (1=semiconductor chip;2,3=electr. connections; 4=conversion phosphor; 7=board). The phosphoris distributed in a binder lens, which at the same time represents asecondary optical element and influences the light emissioncharacteristics as a lens.

FIG. 2: shows a COB (chip on board) package of the InGaN type, whichserves as light source (LED) for white light (1=semiconductor chip;2,3=electr. connections; 4=conversion phosphor; 7=board) The phosphor islocated directly on the LED chip distributed in a thin binder layer. Asecondary optical element consisting of a transparent material can beplaced thereon.

FIG. 3: shows a Golden Dragon® package, which serves as light source(LED) for white light (1=semiconductor chip; 2,3=electr. connections;4=conversion phosphor in cavity with reflector). The conversion phosphoris dispersed in a binder, with the mixture filling the cavity.

FIG. 4: shows an SMD package (surface mounted package) where 1=housing;2, 3=electr. connections, 4=conversion layer. The semiconductor chip iscompletely covered by the phosphor according to the invention. The SMDdesign has the advantage that it has a small design and thus fits inconventional lights.

FIG. 5: shows a diagrammatic representation of a light-emitting diodewhere 1=semiconductor chip; 2, 3=electr. connections; 4=conversionphosphor, 5=bond wire, where the phosphor is applied as top globe in abinder. This form of the phosphor/binder layer can act as secondaryoptical element and influence, for example, the light propagation.

FIG. 6: shows a diagrammatic representation of a light-emitting diodewhere 1=semiconductor chip; 2, 3=electr. connections; 4=conversionphosphor; 5=bond wire, where the phosphor is applied as a thin layerdispersed in a binder. A further component acting as secondary opticalelement, such as, for example, a lens, can easily be applied to thislayer.

FIG. 7: shows an example of a further application, as is already knownin principle from U.S. Pat. No. 6,700,322. The phosphor according to theinvention is used here together with an OLED. The light source is anorganically light-emitting diode 31, consisting of the actual organicfilm 30 and a transparent substrate 32. The film 30 emits, inparticular, blue primary light, generated, for example, by means ofPVK:PBD:coumarine (PVK, abbreviation for poly(n-vinylcarbazole); PBD,abbreviation for2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole). The emission ispartially converted into yellow, secondarily emitted light by a toplayer formed from a layer 33 of the phosphor according to the invention,resulting overall in white emission through colour mixing of theprimarily and secondarily emitted light. The OLED essentially consistsof at least one layer of a light-emitting polymer or of so-called smallmolecules between two electrodes consisting of materials known per se,such as, for example, ITO (abbreviation for indium tin oxide), as anodeand a highly reactive metal, such as, for example, Ba or Ca, as cathode.A plurality of layers are often also used between the electrodes, whichserve either as hole-transport layer or, in the area of small molecules,also as electron-transport layers. The emitting polymers used are, forexample, polyfluorenes or polyspiro materials.

1. Compound of the 6-3-6-4 alkaline-earth metal silicooxynitride typewith europium doping which additionally comprises co-dopants from theseries Th, Ru, Os, F and/or Cl.
 2. Compound according to claim 1,characterised by the formula I(Ca,Sr,Ba)_(6-x)(Si_(1-y)Me _(y))₃(O_(1-z)Ma _(2z))₆N₄:Eu_(x)  (I) whereMe=Th, Ru and/or Os Ma═F and/or Cl x<0.5 y<1 and z<0.1.
 3. Compoundaccording to claim 1, characterised in that x=0.003 to 0.2, y=0.0001 to0.2 and z=0.0005 to 0.03.
 4. Compound according to claim 1,characterised in that x=0.005 to 0.15 and/or y=0.001 to 0.02. 5.Compound according to claim 1, obtainable by mixing silicon nitride-,europium- and calcium- and/or strontium- and/or barium-containingstarting materials with at least one thorium-, osmium-, ruthenium-,fluoride- and/or chloride-containing co-dopant by solid-state diffusionmethods and subsequent thermal aftertreatment.
 6. Process for thepreparation of a compound according to claim 1, having the followingprocess steps: a) preparation of a europium-doped 6-3-6-4 alkaline-earthmetal silicooxy-nitride compound which is co-doped with thorium-,ruthenium-, osmium-, fluoride- and/or chloride-containing materials, bymixing at least 4 starting materials selected from silicon nitride-,europium-, calcium-, strontium-, barium-, thorium-, ruthenium-, osmium-,fluoride- and/or chloride-containing materials, b) thermalaftertreatment of the compound co-doped with thorium, ruthenium, osmium,fluoride and/or chloride. c) washing of the thermally aftertreatedcompounds with an HCl solution and a KOH solution.
 7. Shaped bodycomprising a compound according to claim 1, characterised in that it hasa rough surface which carries nanoparticles comprising SiO₂, TiO₂,Al₂O₃, ZnO, ZrO₂ and/or Y₂O₃ or mixed oxides thereof and/or particlescomprising the compound according to claim 1, with or without dopantsfrom the series europium, thorium, ruthenium, osmium, fluorine and/orchlorine.
 8. Shaped body comprising a compound according to claim 1,characterised in that it has a continuous surface coating consisting ofSiO₂, TiO₂, Al₂O₃, ZnO, ZrO₂ and/or Y₂O₃ or mixed oxides thereof and/orof the compound according to claim 1 without the activator europium. 9.Shaped body comprising a compound according to claim 1, characterised inthat it has a porous surface coating consisting of SiO₂, TiO₂, Al₂O₃,ZnO, ZrO₂ and/or Y₂O₃ or mixed oxides thereof and/or of the compoundaccording to claim 1 with or without dopants from the series europium,thorium, ruthenium, osmium, fluorine and/or chlorine.
 10. Shaped bodycomprising a compound according to claim 1, characterised in that thesurface carries functional groups which facilitate chemical bonding orphysical binding to the environment, preferably consisting of epoxy orsilicone resin.
 11. Process for the production of a shaped bodyaccording to claim 8, having the following process steps: a) preparationof a europium-doped 6-3-6-4 alkaline-earth metal silicooxy-nitridecompound which is co-doped with thorium-, ruthenium-, osmium-, fluoride-and/or chloride-containing materials, by mixing at least 4 startingmaterials selected from silicon nitride-, europium-, calcium-,strontium-, barium-, thorium-, ruthenium-, osmium-, fluorine- and/orchlorine-containing materials, b) thermal aftertreatment of the compoundco-doped with thorium, ruthenium, osmium, fluorine and/or chlorine, c)coating of the surface with nanoparticles comprising SiO₂, TiO₂, Al₂O₃,ZnO, ZrO₂ and/or Y₂O₃ or mixed oxides thereof or with nanoparticlescomprising the compound, with or without dopants.
 12. Process accordingto claim 11, characterised in that process step b) is followed by awashing step with an HCl solution and a KOH solution.
 13. Lighting unithaving at least one primary light source whose emission maximum is inthe range 250 nm to 530 nm, preferably between 350 nm and 500 nm, wherethis radiation is partially or fully converted into longer-wavelengthradiation by a compound and/or phosphor body according to claim
 1. 14.Lighting unit according to claim 13, characterised in that the lightsource is a luminescent indium aluminium gallium nitride, in particularof the formula In_(i)Ga_(j)Al_(k)N, where 0≦i, 0≦j, 0≦k, and i+j+k=1.15. Lighting unit according to claim 13, characterised in that the lightsource is a luminescent compound based on ZnO, TCO (transparentconducting oxide), ZnSe or SiC.
 16. Lighting unit according to claim 13,characterised in that the light source is a material based on an organiclight-emitting layer.
 17. Lighting unit according to claim 13,characterised in that the light source is a plasma or discharge lamp.18. Lighting unit according to claim 13, characterised in that thephosphor is arranged directly on the primary light source and/or remotetherefrom.
 19. Lighting unit according to claim 13, characterised inthat the optical coupling between the phosphor and the primary lightsource is achieved by a light-conducting arrangement.
 20. A phosphorcomprising at least one compound according to claim
 1. 21. A conversionphosphor for the partial or complete conversion of the blue or near-UVemission from a luminescent diode comprising a compound of claim
 1. 22.A conversion phosphor for conversion of the primary radiation into acertain colour point in accordance with the colour-on-demand conceptcomprising a compound of claim
 1. 23. A shaped body according to claim 7which is a phosphor body.